壳聚糖改性4A沸石分子筛颗粒去除低温水中硝酸盐的机理研究
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摘要
为解决我国北方严寒地区常规工艺难以有效去除低温地下水中硝酸盐污染的问题,以4A沸石分子筛为载体,通过壳聚糖改性制备出一种具有低温去除水中硝酸盐功能的吸附颗粒,有望作为吸附剂应用于常规水处理工艺的提标改造.通过小试试验,研究壳聚糖改性4A沸石分子筛颗粒去除低温水中硝酸盐的反应机理,分析其去除硝酸盐过程的吸附动力学、吸附等温线、吸附热力学,并通过pH_(PZC)(零电点)测定、FT-IR (傅里叶红外光谱)和XPS (X射线光电子能谱)进一步分析其反应前、后表面物化特性.结果表明:①在温度为8～10℃下,壳聚糖改性4A沸石分子筛颗粒对硝酸盐的吸附平衡时间为8 h,平衡吸附量为1. 88 mg/g.②吸附过程符合准二级动力学模型,吸附符合Langmuir和Freundlich吸附等温模型,吸附热力学参数ΔG~0<0、ΔH~0>0、ΔS~0> 0,表明吸附为熵增加的吸热过程.③壳聚糖改性4A沸石分子筛颗粒的pH_(PZC)为10. 0,FT-IR结果表明,—NH2和—OH官能团吸附了水中的硝酸根离子,XPS结果表明,N(1s)和O(1s)元素在吸附过程中参与反应.研究显示,壳聚糖改性4A沸石分子筛颗粒分子结构中的—NH2和—OH基团通过静电结合和氢键作用与硝酸根离子进行吸附反应.
A new zeolite molecular sieve modified with chitosan was prepared and investigated for the adsorption of nitrate from underground water at low temperature. The adsorption kinetics,isotherms,and thermodynamics of this adsorbent were studied through batch adsorption experiments of nitrate. The physicochemical characteristics before and after the adsorption reactions were demonstrated by point of zero charge( pH_(PZC)),Fourier infrared spectroscopy( FT-IR) and X-ray photoelectron spectroscopy( XPS) methods. The experimental results showed that:( 1) At the water temperature of 8-10 ℃,the adsorption equilibrium time and adsorption capacity were8 h and 1. 88 mg/g,respectively.( 2) The kinetic study indicated that the pseudo second-order dynamic model could fit the experimental data well and it was also observed that the adsorption isotherms could be well described by both Langmuir and Freundlich isotherm models.The thermodynamic results of ΔG~0< 0,ΔH~0> 0 and ΔS~0> 0 indicated that the adsorption was an endothermic process with increased entropy.( 3) The pH_(PZC)of the particles was 10. 0. And functional groups of —NH2 and —OH were found to adsorb the nitrate ions based on the FT-IR results. N( 1 s) and O( 1 s) elements participated in the reactions during adsorption process according to the XPS results.Studies have shown that the adsorbed nitrate ions were associated with the —NH2 and —OH groups in the molecular structure of the 4 A zeolite molecular sieve modified with chitosan by electrostatic binding and hydrogen bonding. The adsorbents can be applied to the upgrading of the conventional water treatment processes to improve the removal of nitrate in low-temperature groundwater in the cold regions of northern China.
A new zeolite molecular sieve modified with chitosan was prepared and investigated for the adsorption of nitrate from underground water at low temperature. The adsorption kinetics,isotherms,and thermodynamics of this adsorbent were studied through batch adsorption experiments of nitrate. The physicochemical characteristics before and after the adsorption reactions were demonstrated by point of zero charge( pH_(PZC)),Fourier infrared spectroscopy( FT-IR) and X-ray photoelectron spectroscopy( XPS) methods. The experimental results showed that:( 1) At the water temperature of 8-10 ℃,the adsorption equilibrium time and adsorption capacity were8 h and 1. 88 mg/g,respectively.( 2) The kinetic study indicated that the pseudo second-order dynamic model could fit the experimental data well and it was also observed that the adsorption isotherms could be well described by both Langmuir and Freundlich isotherm models.The thermodynamic results of ΔG~0< 0,ΔH~0> 0 and ΔS~0> 0 indicated that the adsorption was an endothermic process with increased entropy.( 3) The pH_(PZC)of the particles was 10. 0. And functional groups of —NH2 and —OH were found to adsorb the nitrate ions based on the FT-IR results. N( 1 s) and O( 1 s) elements participated in the reactions during adsorption process according to the XPS results.Studies have shown that the adsorbed nitrate ions were associated with the —NH2 and —OH groups in the molecular structure of the 4 A zeolite molecular sieve modified with chitosan by electrostatic binding and hydrogen bonding. The adsorbents can be applied to the upgrading of the conventional water treatment processes to improve the removal of nitrate in low-temperature groundwater in the cold regions of northern China.
引文
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[15]LI S,YUAN Z,GONG W,et al.The mechanism study of trace Cr(VI)removal from water using Fe0,nanorods modified with chitosan in porous anodic alumina[J].Applied Surface Science,2015,328:606-613.
[16]WANG J,XU W,CHEN L,et al.Preparation and evaluation of magnetic nanoparticles impregnated chitosan beads for arsenic removal from water[J].Chemical Engineering Journal,2014,251:25-34.
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[19]魏蛲,程诚,吕龙,等.交联壳聚糖季铵盐对水体中硝酸盐的吸附去除研究[J].水处理技术,2012,38(9):21-25.WEI Nao,CHENG Cheng,LV Long,et al.Adsorption of nitrate from water by cross-linked quaternary chitosan salt[J].Technology of Water Treatment,2012,38(9):21-25.
[20]HARIKISHORE D,REDDY K,LEE S M,et al.Removal of Cd(II)and Cu(II)from aqueous solution by agro biomass:equilibrium,kinetic and thermodynamic studies[J].Environmental Engineering Research,2012,17(3):125-132.
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[24]张聪璐,胡筱敏,赵研,等.磁性壳聚糖衍生物对阴离子染料的吸附行为[J].环境科学,2015(1):55-56.ZHANG Conglu,HU Xiaomin,ZHAO Yan,et al.Adsorption behavior of anionic dyes onto magnetic chitosan derivatives[J].Environmental Science,2015(1):55-56.
[25]KONG J,YUE Q,SUN S,et al.Adsorption of Pb(II)from aqueous solution using keratin waste:hide waste:equilibrium,kinetic and thermodynamic modeling studies[J].Chemical Engineering Journal,2014,241(4):393-400.
[26]董炎明,王勉,吴玉松,等.壳聚糖衍生物的红外光谱分析[J].纤维素科学与技术,2001,9(2):42-56.DONG Yanming,WANG Mian,WU Yusong,et al.Infrared spectroscopic analysis of chitosan derivatives[J].Cellulose Science and Technology,2001,9(2):42-56.
[27]BANU H T,MEENAKSHI S.One pot synthesis of chitosan grafted quaternized resin for the removal of nitrate and phosphate from aqueous solution[J].International Journal of Biological Macromolecules,2017,104:1517-1527.
[28]SHEN C,WU L,CHEN Y,et al.Efficient removal of fluoride from drinking water using well-dispersed monetite bundles inlaid in chitosan beads[J].Chemical Engineering Journal,2016,303:391-400.
[29]HU Q,CHEN N,FENG C,et al.Nitrate removal from aqueous solution using granular chitosan-Fe(III)-Al(III)complex:kinetic,isotherm and regeneration studies[J].Journal of the Taiwan Institute of Chemical Engineers,2016,63:216-225.
[30]TEIMOURI A,NASAB S G,VAHDATPOOR N,et al.Chitosanzeolite y-nano Zr O2nanocomposite as an adsorbent for the removal of nitrate from the aqueous solution[J].International Journal of Biological Macromolecules,2016,93:254-266.
[31]XIE Y,LI S,LIU G,et al.Equilibrium,kinetic and thermodynamic studies on perchlorate adsorption by cross-linked quaternary chitosan[J].Chemical Engineering Journal,2012,192(2):269-275.
[2]环境保护部.2016中国环境状况公报[R].北京:环境保护部,2016:1-54.
[3]郑立辉,刘亭亭,苑庆山.基于常规处理的微污染水源水处理工艺改进措施[J].中国环境管理干部学院学报,2014(1):61-64.ZHENG Lihui,LIU Tingting,YUAN Qingshan.Improved processes of micro-polluted source water based on traditional water process[J].Journal of Environmental Management College of China,2014(1):61-64.
[4]孙美乔,郜玉楠,傅金祥,等.壳聚糖改性强化混凝处理低温氨氮污染水源水研究[J].给水排水,2017(7):67-71.SUN Meiqiao,GAO Yunan,FU Jinxiang,et al.Treatment of low temperature,ammonia-nitrogen contaminated water by enhanced coagulation with modified chitosan[J].Water&Wastewater Engineering,2017(7):67-71.
[5]金赞芳,李文腾,潘志彦,等.地下水硝酸盐去除方法[J].水处理技术,2006,32(8):34-37.JIN Zanfang,LI Wenteng,PAN Zhiyan,et al.Methods for nitrate removal from underground water[J].Technology of Water Treatment,2006,32(8):34-37.
[6]张世春,王恩文,雷绍民,等.沸石分子筛在大气与水污染治理应用的研究进展[J].无机盐工业,2014,46(11):9-12.ZHANG Shichun,WANG Enwen,LEI Shaomin,et al.Application research progress of zeolite molecular sieve in air and water pollution control[J].Inorganic Chemicals Industry,2014,46(11):9-12.
[7]LIU X,WANG R.Effective removal of hydrogen sulfide using 4Amolecular sieve zeolite synthesized from attapulgite[J].Journal of Hazardous Materials,2017,326:157-164.
[8]ARORA M,EDDY N K,MUMFORD K A,et al.Surface modification of natural zeolite by chitosan and its use for nitrate removal in cold regions[J].Cold Regions Science&Technology,2010,62(2/3):92-97.
[9]WIDIASTUTI N,WU H,MING A,et al.The potential application of natural zeolite for greywater treatment[J].Desalination,2008,218(1):271-280.
[10]BHATNAGAR A,SILLANPAA M.Applications of chitin-and chitosan-derivatives for the detoxification of water and wastewater:a short review[J].Advances in Colloid&Interface Science,2009,152(1/2):26.
[11]常青,韦俊.壳聚糖季铵盐絮凝剂处理丁苯橡胶废水的研究[J].中国环境科学,2012,32(2):232-237.CHANG Qing,WEI Jun.Preparation of chitosan quaternary ammonium and flocculation of styrene-butadiene rubber wastewater[J].China Environmental Science,2012,32(2):232-237.
[12]BRATSKAYA S Y,AZAROVA Y A,Matochkina E G,et al.N-(2-(2-pyridyl)ethyl)chitosan:synthesis,characterization and sorption properties[J].Carbohydrate Polymers,2012,87(1):869-875.
[13]TEIMOURI A,GHANAVATINASAB S,HABIBOLLAHI S,et al.Synthesis and characterization of a chitosan/montmorillonite/ZrO2nanocomposite and its application as an adsorbent for removal of fluoride[J].Rsc Advances,2014,5(9):6771-6781.
[14]WANG J,CHEN C.Chitosan-based biosorbents:modification and application for biosorption of heavy metals and radionuclides[J].Bioresource Technology,2014,160(5):129-141.
[15]LI S,YUAN Z,GONG W,et al.The mechanism study of trace Cr(VI)removal from water using Fe0,nanorods modified with chitosan in porous anodic alumina[J].Applied Surface Science,2015,328:606-613.
[16]WANG J,XU W,CHEN L,et al.Preparation and evaluation of magnetic nanoparticles impregnated chitosan beads for arsenic removal from water[J].Chemical Engineering Journal,2014,251:25-34.
[17]胡启立.金属负载壳聚糖颗粒去除水中硝酸盐及吸附动力学研究[D].北京:中国地质大学(北京),2016.
[18]朱华跃,蒋茹,钱勇兴.质子化交联壳聚糖颗粒对水体中硝酸盐的吸附去除作用[J].安徽农业科学,2008,36(7):2919-2921.ZHU Huayue,JIANG Ru,QIAN Yongxing.Study on the adsorptiona and removal of protonated cross-linked chitosan granules to nitrate in water body[J].Journal of Anhui Agricultural Sciences,2008,36(7):2919-2921.
[19]魏蛲,程诚,吕龙,等.交联壳聚糖季铵盐对水体中硝酸盐的吸附去除研究[J].水处理技术,2012,38(9):21-25.WEI Nao,CHENG Cheng,LV Long,et al.Adsorption of nitrate from water by cross-linked quaternary chitosan salt[J].Technology of Water Treatment,2012,38(9):21-25.
[20]HARIKISHORE D,REDDY K,LEE S M,et al.Removal of Cd(II)and Cu(II)from aqueous solution by agro biomass:equilibrium,kinetic and thermodynamic studies[J].Environmental Engineering Research,2012,17(3):125-132.
[21]MASHEANE M L,NTHUNYA L N,MALINGA S P,et al.Chitosanbased nanocomposites for de-nitrification of water[J].Physics&Chemistry of the Earth,2016,100:1-13.
[22]PERIASAMY K,NAMASIVAYAM C.Removal of nickel(II)from aqueous solution and nickel plating industry wastewater using an agricultural waste:peanut hulls[J].Waste Management,1995,15(1):63-68.
[23]AZIZ A S A,MANAF L A,MAN H C,et al.Kinetic modeling and isotherm studies for Copper(II)adsorption onto palm oil boiler mill fly ash(POFA)as a natural low-cost adsorbent[J].Bioresources,2013,9(1):336-356.
[24]张聪璐,胡筱敏,赵研,等.磁性壳聚糖衍生物对阴离子染料的吸附行为[J].环境科学,2015(1):55-56.ZHANG Conglu,HU Xiaomin,ZHAO Yan,et al.Adsorption behavior of anionic dyes onto magnetic chitosan derivatives[J].Environmental Science,2015(1):55-56.
[25]KONG J,YUE Q,SUN S,et al.Adsorption of Pb(II)from aqueous solution using keratin waste:hide waste:equilibrium,kinetic and thermodynamic modeling studies[J].Chemical Engineering Journal,2014,241(4):393-400.
[26]董炎明,王勉,吴玉松,等.壳聚糖衍生物的红外光谱分析[J].纤维素科学与技术,2001,9(2):42-56.DONG Yanming,WANG Mian,WU Yusong,et al.Infrared spectroscopic analysis of chitosan derivatives[J].Cellulose Science and Technology,2001,9(2):42-56.
[27]BANU H T,MEENAKSHI S.One pot synthesis of chitosan grafted quaternized resin for the removal of nitrate and phosphate from aqueous solution[J].International Journal of Biological Macromolecules,2017,104:1517-1527.
[28]SHEN C,WU L,CHEN Y,et al.Efficient removal of fluoride from drinking water using well-dispersed monetite bundles inlaid in chitosan beads[J].Chemical Engineering Journal,2016,303:391-400.
[29]HU Q,CHEN N,FENG C,et al.Nitrate removal from aqueous solution using granular chitosan-Fe(III)-Al(III)complex:kinetic,isotherm and regeneration studies[J].Journal of the Taiwan Institute of Chemical Engineers,2016,63:216-225.
[30]TEIMOURI A,NASAB S G,VAHDATPOOR N,et al.Chitosanzeolite y-nano Zr O2nanocomposite as an adsorbent for the removal of nitrate from the aqueous solution[J].International Journal of Biological Macromolecules,2016,93:254-266.
[31]XIE Y,LI S,LIU G,et al.Equilibrium,kinetic and thermodynamic studies on perchlorate adsorption by cross-linked quaternary chitosan[J].Chemical Engineering Journal,2012,192(2):269-275.
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